Micrometrically Controlled Surface Modification of Teflon ^® by Redox Catalysis: Electrochemical Coupling between Teflon ^® and a Gold Band Ultramicroelectrode

Abstract

Carbon-fluorine bonds of Teflon (polytetrafluoroethylene, PTFE) can be reduced electrochemically with the purpose of modifying its adhesive and wetting surface properties by micrometrically controlled surface carbonization of the material. This can be performed adequately by redox catalysis provided that the redox mediator couple has a sufficiently negative reduction potential. The process is investigated kinetically with benzonitrile as the mediator and a gold-band ultramicroelectrode mounted adjacent to a PTFE block, though separated from it by an insulating micrometric mylar gap. For moderate fluxes of reduced mediator, the whole device behaves as a generator-collector double-band assembly with a constant current amplification factor. This is maintained over long periods of time, during which the carbonized PTFE zones extends over distances that are much wider than the slowly expanding cylindrical diffusion layer generated at the gold-microband electrode. This establishes that the overall redox catalysis proceeds through electronic conduction in the n-doped carbonized material. Thus, carbonization progresses at the external edge of the freshly carbonized surface in a diffusion-like fashion (dependence on the square root of time), while the redox-mediator oxidized form is regenerated at the carbonized PTFE edge facing to the gold ultramicroelectrode, so that the overall rate of carbonization is controlled by solution diffusion only. For larger fluxes of mediator, the heterogeneous rate of reduction and doping of PTFE becomes limiting, and the situation is more complex. A conceptually simple model is developed which predicts and explains all the main dynamic features of the system under these circumstances and allows the determination of the heterogeneous rate constant of carbon-fluorine bonds at the interface between the carbonized zone and the fresh PTFE. This model can be further refined to account for the effect of ohmic drop inside the carbonized zone on the heterogeneous reduction rate constants and henceforth gives an extremely satisfactory quantitative agreement with the experimental data.

Scanning electrochemical microscopy of one-dimensional nanostructure: Effects of nanostructure dimensions on the tip feedback current under unbiased conditions

“…Steady-state diffusion without a convection effect as assumed in our model is a good approximation for quasi-steady-state hemicylindrical diffusion at a long nanoband [6-9] under the SECM configuration. The hemicylindrical diffusion layer with the thickness that is controlled by the band width and height is developed not only at the region of the nanoband surface under the tip (Figure 4a) but also at the region exposed to the bulk solution (Figures 4b).…”

“…Traditionally, such electrodes with both nanoscale and macroscale dimensions have been explored in electroanalytical chemistry [5] because of the unique mass transfer properties of the high-aspect-ratio electrodes [6-9]. The anisotropic nanoelectrodes give a large and easily measurable faradic current, which varies with the macroscopic dimension.…”